Waterproofing composition



Patented Nov. 21, 1 939 WATERPROOFING COMPOSITION Arthur F. Taggart,Scarsdale, and Warley'L. Parrott, New York, N. Y.

No Drawing. Application April 22, 1937,

. Serial No. 138,364

4 Claims. (01. 134-13) Our invention relates to waterproofingcompositions, and more particularly to waterproofing compositions thatform, upon evaporation of their volatile constituents, fine-grained toglass-like 5 water-repellent films.

One of the features of" our invention is the crystallization of awater-repellent crystalline material in the composition controlled by anoncrystalline water-repellent constituent present in o thickened form,whereby the normal growth of the crystals of the controlled material isarrested and that material deposits in the form of extremely fine sizecrystals. These fine crystals uniformly and intimately admix with thefine size particles of the controlling non-crystalline substance to formupon complete, solidification a continuous fine-grained to glass-likefilm the imperforate nature of which prevents moisture penetration.

Preliminarily to the discovery upon which our invention is based, weprepared and observed microscopically numerous slides of differentmixtures of water-repellent substances and tested these mixtures forcomparative waterproofing effectiveness. We observed from these teststhat the most effective waterproofing mixtures, whatever the ingredientsused, were those that produced uniform fine-grained to glasslike films.Such films, generally speaking, are

composed of ingredients that are so finely divided that no definitecrystalline structure can be detected in the film when it is viewedthrough a microscope with dark field'illumination and having amagnification of about 150 diameters. Following these observations, wediscovered that highly eificient waterproofing compositions capable ofproducing the desired fine-grained to glass-like films may beconsistently produced by admixing in the proper proportions an organicforming material, and a water-repellent, substance that will cause thesolvent and this substance to thicken sufliciently, before the crys- 45tallizable material begins to crystallize, to arrest the growth ofcrystals when the crystalliz- 55 An object of ou in en n s t p ovide asolvent,- an organic water-repellent crystal-' waterproofing compositioncontaining an in'timate admixture of various water-repellentconstituents so related in solubility in the solvent used and inconcentration therein, that whatever the constituents usedthe-composition will 5 form, upon evaporation of its volatileconstituents, a highly water-repellent fine-grained t glass-like film.

From the numerous microscopic observations that we have made of variouswaterproofing 10 compositions, we have noticed that if the compositiondoes not contain, at the time of crystallization of the crystallizablewater-repellent constituents, .a constituent that will interfere Y withthe normal crystal growth of the ,crystalliz- 1 able material, thelatter will deposit in the form of relatively large, irregular andseparated crystals. The films produced by such compositions arenon-uniform and have a porphyritic or per-' forated structure thatpermits moisture penetra- 20 tion. These films are not satisfactorysince they do not completely waterproof the-materials to which they areapplied. On the other hand, we have found that if thesolvent andwaterrepellent constituents are properly chosen and 25 theirconcentrations properly regulated to effect the above mentioned crystalgrowth interference, the compositions will produce upon solidificationuniform, fine-grained to glass-like, imperforate, highly water-repellentfilms. 30

The rule or formula to be followed for producing the improvedwaterproofing compositions of our invention comprises selecting anorganic solvent, acrystallizable water-repellent material, and-anormally solid or viscous sub 35 stance (preferably water-repellent) andthat is chemically or physically so related that the mixture of thissubstance and the solvent will thicken upon concentration thereof; andto so proportion them that the thickening will occur 40 before thecrystallizable water-repellent constituent or constituents in the liquidwaterproofing composition begin to'crystallize. In other words, when thewaterproofing composition is applied to a material to be waterproofedand the organic solvent begins' to evaporate, one of the constituentsmust first cause this substance and the solvent to thicken, either inthe form of a gel or' a viscous mass, so that when the crystallizablewater-repellent material subsequently begins to precipitate out ofsolution the thickener and solvent will be in thickened form to arrestthe normal crystal growth of the precipitate so that the crystals ofwater-repellent material will be deposited in extremely fine size form,connormally fine size or amorphous particles of the water-repellentthickener to produce upon the material to be waterproofed a compositefinegrained to glass-like water-repellent film.

One of theimportant and commercially valuable features of our inventionis that the waterproofing composition may be made from any two or morewater-repellent constituents and a suitable solvent properly selectedfrom large groups of such constituents subsequently denoted herein and,in general, the same degree of waterproofing effectiveness will beobtained in each case. Regardless of the constituents so selected, theirmaximum waterproofing effectiveness will always be produced so long asthe crystallization of the crystallizable water-repellent material is.properly controlled to produce very fine size crystals and therebyfine-grained films.

Accordingly, a'number of watererepellent constituents wliich heretoforehave been considered in ,someirespects undesirable, such as for example,

paraffin, waxes, and gums, may now be used as constituents in highlyeffective waterproofing compositions. As aresult, the field of effectivewaterproofing compositions has been markedly extended.

While the exact water resistance of compositions produced from variousmixtures of the selected water-repellent constituents will vary somewhatinherently, they will each possess a high degree of water-repellencybecause of the fine-grained, uniform, compact structure of theirdeposited films. That is to say, these films are composed of extremelysmall particles so uniform in size, admixture and distribution that thefilm is practically homogeneous and substantially free of interstices.Consequently, the film ofiers a uniform high resistance to water overits entire surface and being practically nonporous it is impervious towater penetration.

' In view of the fact that the only essential requirement for producingthe desired type of waterproofing composition is proper selection of awater-repellent substance that with the solvent will thickensufiiciently at the proper concentrations to arrest the crystal growthofthe water-repellent crystalizable material, it will be apparent thatwide variations may be made in the several constituents used inthewaterproofing composition as illustrated by the following.

The crystallizable water-repellent material, which constitutes one ofthe principal waterproofing ingredients in the composition, may be anyorganic water-repellent material that will. crystallize uponconcentration in an organic sol Some of the water-repellent crystalliz-'vent. able materials that we have found satisfactory are as follows:

Fatty materials, e. g., both those natural fats I and the.artificiallysaturated animal, vegetable and marine fats and oils which crystallizeand are substantially solid at normal atmospheric temperatures; such aslard, tallow, cocoa butter, fish and whale fats, hydrogenated animaloil, cotton seed, corn, cocoanut, peanut, fish and whale oils.

Fatty acid glycerides, e. g., both those natural glycerides and thoseartificially saturated jglyi'cerides'of the higher fatty acids found inani-- -m al',' vegetable and marine: fats which crystalli'ze a n'd aresubstantially solid at normal at- "mosbheric temperatures, e. g.,hydrogenated fish oil glycerides.

Higher fatty acids; -e. g., both those natural acids and thoseartificially saturated fatty acids tially solid at normal atmospherictemperatures,

e. g., cholesterol, and camphor.

Hydrocarbons; e. g., paraflin, montan, ceresin, and others which aresubstantially solid at normal atmospheric temperatures.

The solvent used may be any one of the organic evaporative solvents thatwill act as a common solvent for the water-repellent thickener and thecrystallizable material; and with the thick- Benzol Tolulol XylolNitrobenzene 3. Oils derived by steam distillation of resinous woods; e.g., turpentine 4. Halogen derivatives of lower hydrocarbons;

Carbon tetrachloride Chloroform Ethylene-dichloride 5. Cellosolve Thethickener may be any organic, preferably waterproof, substance that withthe solvent will thicken at the proper concentration to arrest thecrystal -growth of the crystallizable waterrepellent material. We havefound it advantageous to use water-repellent substances as thickeners.These substances are of the type normally considered as amorphous,although X-ray analyses might show some or all of these I substances tohave, at least in part, a crystalline structure. We appreciate-that anywaterproof substance whether of an organic or inorganic nature andwhether of a crystalline or non-crystalline character, could be used asthe thickener in accordance with our invention provided it served thepurpose of controlling the crystal growth of the definitely crystallinewater-repellent material or materials used in the composition. Theprincipal requirement for the thickener is that regardless ofitschemical nature, the solvent and the thickener it will increase inviscosity at the proper concentration and time to effect the desiredcrystal growth control. The thickener may be either of a gel-formingtype or of a non-gel-forming type. As far as the physical character ofthe thickener is concerned, it is only necessary that it and the solventwill be 'sufiiciently viscous tophysically interfere with the normalcrystal growth of the crystallizable water-repellent material.

Examples of thickeners that we have found Satisfactory or use in. ourinvention are the following:

35 mation of fine-grain films are as follows:

Example I Y Per cent Aluminum'stearate (thickener) 2.0 3.0 Hydrogenatedfish oil glycerides (crystallizable material) 1.0- 3.0 Petroleum naphtha(solvent) .1 96.5 93.5 Cresol (thinner) 0.5- 0.5

100.0-100.0 Example II Per cent Cumar (thickener) 80.00 Paraffin(crystallizable material) 0.75 50 Hydrogenated naphtha (solvent) 19.25

100.00 Example III L Grams 55 Asphalt (thickener) 20-25 5 ficialasphalt.

Gums and resins; e. g., both the natural products such as rosin, copal,colophony, dammer,

and the artificial neutral products such as the cumars.

cement.

Cellulosic materials; e. g., collodion (tetranitrate of cellulose).

when the thickener used in the waterproofing compositionforms a gel orgel-like mass initially in the hydrocarbon solvent, i. e., beforeconcentration in the solvent, we have found it desirable to use athinner or dispersing agent to disperse the gel and produce a mobilecolloidal solution. This initial breaking or dispersing of the gel] willnot, however, if the proper dispersing agent is used, prevent thedesired formation of gel or viscous mass for crystal growth controlduring evaporation-of the solvent when the composition is used.The-thinner used for dispersing the initial gel should be a substancethat volatilizes on evaporation of the mixture. Examples of the thinnersor dispersing agents that we have found satisfactory are the following:Methyl, ethyl, butyl and amyl alcohols, phenol, cresol, aniline,toluidine, acetone and acetic acid.

Examples of various waterproofing composi-- tions illustrating theproportions of ingredients necessary for crystal growth control and thefor- Hydrogenated fish oil glycerides (crystallizable material)Hydrogenated fish oil acids (crystallizable material) 1. 3

Hydrogenated naphtha (solvent) 100 Example IV Per cent Aluminum stearate1.85

Hydrogenated fish oil glycerides 1.00-

Carbon tetrachloride 96.15

Ethyl alcohol 1.00

100.00 Example V Duco" cellulosic cement (thickener) c.v c 15Hydrogenated fish oil glycerides (crystallizable material) ,gram 0.1Acetone (solvent) c. c

75 Hydrogenated naphtha (solvent) c.c 5

Hydrocarbons; e. g., rubber, Duco household Example VI Collodionsolution consisting of tetra-nitrate of cellulose, ethyl alcohol andethyl ether (thickener) c.'c 5 Cholesterol (crystallizable material)gram 0.025 Example VII Collodion solution consisting of tetra-nitrate ofcellulose, ethyl alcohol and ethyl ether (thickener) c. c 5 'Camphor(crystallizable material) gram 0.3

Example VIII Per cent Aluminum stearate (thickener) 3 Cumar (thickener)5.0 Hydrogenated fish oil glycerides (crystallizable material) 2.7Hydrogenated fish oil. acids (crystallizable material) 0.3 Hydrogenatednaphtha (solvent) 88.0 Ethyl alcohol (thinner) 1 It is to be understoodthat the above examples are'not to limit the scope of our invention andthatvarious other compositions may be prepared utilizing some of theother solvents, thickeners, crystallizable water-repellent materials,and thinners or dispersing agents listed hereinabove, and variouscombinations of these and like materials having the necessarycharacteristics above described for producing the fine-grain toglass-like films characteristic of our invention.

The tests that we have found satisfactory to determine suitable solventsand thickeners (that.

is those capable of producing upon concentration a marked increase inviscosity-,sufiicientto interfere with the normal crystaljigrowth of thecrystallizable water-repellent material and proper proportions thereof),are as follows: A mixture is made of the thickener and thegs olvent thatare desired to be used, and the mixture concentrated by evaporation tothe point. at which the mixture shows a marked increase" in viscositysuch as attended by gel formation or a definite tendency to string. Ifthe mixture either gels or strings, the solvent and thickener aresuitable.

The concentration of the solvent in the mixture when it reaches thispoint is then noted. Next,

a mixture of a water-repellent crystallizable. material and solvent ismade and evaporated to the point at which precipitation of thecrystallizable material begins. The concentration of solvent in themixture at this'point is noted;

If, at the above mentioned points of gelling or stringing andj crystallizing, the concentration of the solvent -in the mixture of thecrystallizable material and solvent is-a'ppreciably less than theconcentration of the solvent in the mixture of the thickener andsolvent, the relative propororder to delay its precipitation and therebyinl tions of thickener and crystallizable material are substantiallycorrect. If the concentrations of sure precipitation. of the thickenerbefore pre-.

cipitation of the crystallizable material. If the mixture of thickenerand. solvent gels or strings at a concentration of solventdess than theconcentration of solvent in the mixture of crystallizexamination, suchas the following: A drop of the waterproofing composition containing thesolvent, the water-repellent thickener, and the water-repellentcrystallizable material is placed on' a slide and examined aftersolidification under a microscope with dark field illumination and amagnification of about 150 diameters. If under .these conditions thefilm appears fine-grained to glass-like, it is a satisfactorywaterproofing film,

indicating that the crystal growthof the crystallizable water-repellentmaterial has been properly arrested by the thickener.

However, if definite crystals are scattered in porphyritic fashionthroughout the mass of the film, the proportion of crystallizablematerial in the mixture is too high. A new mixture with slightly smallerproportion of crystallizable material should then be tried until asatisfactory film is obtained. Alternatively, the same efiect can beproduced in some instances, by adding to the composition a certainproportion of another miscible solvent in which the crystallizablematerial is more soluble and the thickener not more soluble. Forexample, when using the Duco" cement as the thickener with acetone asthe solvent, a proportion of 0.1 gram of hydrogenated fish oilglycerides to 5 c. c. of cement gave a porphyritic structure. By addingto the mixture 1 c. c. of hydrogenated naphtha, which is a good solventfor the glycerides,, the film prepared with the same proportion ofglycerides and cement was non-porphyritic; in other words, amorphous andglass-like.

In all of the compositions mentioned above, it will be understood thatthe proper proportioning of the thickener and the crystallizablematerials is essential. The actual amounts of thickener andcrystallizable material may vary from any useful small amount vup to theamounts just a short of those that would normally form supersaturatedsolutions, that is, amounts suflicient to cause precipitation of thesolids in the waterproofing composition before it is applied for use. Inother words, the fine-grained to glass-like films are produced byprecipitation from solution, and any desired amounts of materials lessthan the amount that will not go into solution may be used. The actualamounts of thickener and crystallizable materials used will dependlargely upon the thickness of the waterproofing film that it. is desiredto produce and upon the degree of penetration required. The thickness ofthe film is proportional to the amounts of solid materials present inthe composition. Thepenetrativeness of the composition is inverselyproportional to the concentration of solids therein, the greater theconcentration of solids the smaller the penetrativeness of thecomposition and vice versa.

\ The waterproofing compositions of our invention may be appliedaccording to any well known methods, such as brush, spray, and immersionprocesses.

The waterproofing compositions of our invention may be prepared by anysuitable admixing of the several constituents, once the properproportions thereof have been determined in the manner describedhereinabove. For example, the thickener and the crystallizable materialmaybe \admixed in solid form and heated until at least one of thematerials liquefies and causes all of the solids to mutually dissolve.The proper amount of solvent is then added to this mixture of thethickener and crystallizable material. If the thickener used is of thegel forming type, a relatively small amount, such as for example 1% orless of the thinner or dispersing agent is added to the mixture, eitherbefore or after the solvent is added, for the purpose of producing athin penetrative mobile type of solution suitable for brushing, sprayingor dipping processes.

Another method ofpreparing the composition comprises dissolvingsimultaneously the thickener and crystallizable material in the solvent,applying heat and agitation, if necessary, to effect so lution of thesolids in the solvent. Still another method of preparing thecomposition, when using as the thickener a gel-forming material,comprises heating the thickener and solvent mixture until a gel isformed, then adding to the' gel a relatively small amount of thedispersing agent to disperse the gel into a mobile colloidal solution,and then dissolving in this solution thec'rystallizable material.

From these examples it will be apparent that various other methods ofpreparing the compositions may be used and our invention is intended tocover any and all of such methods.

It is to m understood that the doctrine of equivalents applies with fullforce and effect to this application and the invention disclosed hereinand that various modifications and changes may be made in the materialsand methods used without departing from the scope of this invention. Theappended claims are directed to some of the novel features of theinvention.

We claim:

1. A mobile, liquid, penetrative waterproofing composition comprising anormally solid hydrogenated fish oil, a petroleum naphtha and a volatileconstituents a fine-grained to glass-like water-repellent film,comprising a normally solid water-repellent crystallizable organicmaterial selected from the group consisting -of fats and waxes oforganic origin, an evaporating hydrocarbon solvent, and anaturalasphalt, mixed in such proportions that upon concentration 'ofthe composition said natural asphalt and hydrocar-- bon solvent willthicken before said crystallizable material beings to precipitate,whereby said natural asphalt arreststhe normal crystal growth of thecrystallizable material as it precipitates from said solvent, and causessaid crystallizable material to precipitate in the form of extremelyfine size crystals.

3. A mobile, liquid, penetrative waterproofing composition that formsupon evaporation of its volatile constituents a fine-grained toglass-like water-repellent film, comprising a normally solidwater-repellent crystallizable organic material selected from the groupconsisting of fats and waxes of organic origin, an evaporative organicsolvent, and asphalt, mixed in such proportions that upon concentrationof the composition saidasphalt and organic solvent will thicken before 7said crystallizab le material to precipitate,

whereby said asphalt arrests the normal crystal growth of thecrystallizable material as it precipitates from said solvent, and causessaid crystallizable material to precipitate in the form of extremelyfine size crystals.

4. A mobile, liquid, penetrative waterproofing composition that formsupon evaporation of its volatile constituents a fine-grained to 'glasslike water-repellent film, comprising a normally solid water-repellentcrystallizable material, an evapoporative organic solvent, an anasphaltic substance, mixed in such proportions that upon concentrationof the composition said a'sphaltic substance and organic solvent willthicken before said crystallizable material begins to precipitate,whereby said asphaltic substance arrests the normal crystal growth ofthe crystallizable material as it precipitates from said solvent, andcauses-said crystallizable material to precipitate in the form ofextremely fine size crystals.

AR'I'HUR F. :TAGGART. WARLEY L. PARRO'I'I.

- CERTIFICATE OF CORRECTION, Patent No. 2,180,971. November 21, 1959.

ARTHUR F. TAGGART'.

It is hereby certified that'error appears in the printed specificationof the above mgmbered patent requiring; correction as follows: Page Lsecond column, line 55, claim 2, for the word "evaporating" readevaporative;

'page 5, first column, line 12, claim 11., for F'an an read arid an; andthat th said Letters Patent should; be read with this. correctiontherein that the seine may oon form to therecord of the ,case in thePatent Office.

Sigped and sealed this 26th day of December, A. D.---1959.

Henry Van Arsdale,

(Seal) Acting Comxnissioner of Patents.

